JPS6143155A - Cyclohexanone derivative, manufacture and herbicide - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application: The present invention relates to a cyclohexenone derivative, a method for producing the same, and a herbicide containing the compound as an active substance.

PRIOR ART It is known to use rainbow clohexenone derivatives to control undesirable grasses in cultivated plants (German Patent Application No. 243,910).
Specification No. 4). Furthermore, it is known from German Patent Application No. 3248554 that cyclohexenon-1-one derivatives having a para-substituted phenyl ring in the 5-position control grass weeds in corn and wheat. It is.

Effect: By the way, formula (■): [In the formula, R1 is a hydrogen atom, a methoxycarbonyl group, an ethoxycarbonyl group, a methyl group or a cyano group, and RQt 1
represents an alkyl group having ~4 C-atoms, R3 represents an alkyl group having 1 to 4 C-atoms, an alkenyl group having 3 or 4 C-atoms, an alkenyl group having 3 or 4 C-atoms; represents a halogenated alkenyl group or propargyl group having an atom and 1 to 3 halogen substituents, R4 represents a hydrogen atom or an alkyl group having 1 to 4 C-atoms, R5 represents a hydrogen atom, an alkyl group aliphatic acyl having 2 to 8 C-atoms, formyl, cycloalkylcarbonyl having 4 to 7 C-atoms, methoxyalkylcarbonyl, nitro, halogen, alkyl or alkoxy; 5 to 8 ℃ optionally substituted benzoyl group, alkoxycarbonyl group, benzyloxycarbonyl group, phenoxycarbonyl group, alkylthiocarbonyl group, N,N-dialkylcarbamoyl group, N-alkylcarbamoyl group, cycloalkyl group C-
N-cycloalkylcarbamoyl group, N-
Alkoxy-N-alkylcarbamoyl group, N-phenylcarbamoyl group optionally substituted by nitro, halogen, alkyl, alkoxy or haloalkyl, alkylsulfonyl group, alkenylsulfonyl group,
10genated alkylsulfonyl group, N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group,
N-acyl-N-alkylsulfamoyl group, N-alkyl-N-methoxycarbonylsulfamoyl group, dialkoxyphosphoryl group, dialkoxythiophosphoryl group, having 2 to 5 C-atoms in the acyl group, 2 - represents an alkanoyl group, an acyloxyacetyl group, or an alkoxyoxalyl group, and R6 is an alkyl group, an alkyl group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkylthio group, an alkylsulfinyl group, an alkylsulfonyl group, a nitro cyclohexenone derivatives and salts of these compounds are particularly suitable for use in plants of the grass family (Graminaceae).
It was found that it has a good herbicidal effect against the species from A. mlnaer). This compound is both tolerable and selective in cultivated plants of the grass family as well as in monocotyledonous plants not counted among the grasses. Sara K
, among which some compounds also behave selectively in cultivated grasses, such as wheat and rice, and at the same time control undesirable grasses.

The cyclohexenone derivatives of formula (1) can occur in a number of forms, all encompassed by the claims: In formula (1), 11 is a hydrogen atom, a methoxycarbonyl group, an ethoxycarbonyl group, a methyl or a cyan group, in which case a hydrogen atom is preferred.

In formula (1), B2 is an unbranched or branched alkyl group having 1 to 4 C atoms, i.e. a methyl group;
It represents an ethyl group, n-propyl group, isopropyl group, n-butyl group, nibutyl group, isobutyl group, and tertiary butyl group. Alkyl groups of 2 or 3 C atoms are preferred.

The group for R3 in formula (1) is gulonokurgyl, 1-
4 C-atoms M alkyl, 3 or 4 C-atoms
- Alkenyl commanding atoms or alkyl groups containing up to three halogen substituents are preferred 0 Groups for R3 in formula (1), gulonokurugyl, 1
-alkyl with 4 C-atoms, alkenyl with 3 or 4 C-atoms or 1-3 or 4-C-atoms which can contain up to 3 halogen substitutions Alkenyl rogenyl, % chloralkenyl, such as methyl, ethyl, n-propyl, isopropyl, n-fflL', nibutyl, isobutyl, tert-butyl, allyl, l-chloroprop-1-en-3-yl, 2-chloroprop-1-en-3-yl, 1.3-dichloroprop-1-en-3-yl, and 1.1.2-trichloroprop-1-en-3-yl.

The group for R4 in formula (1) is a hydrogen atom or an alkyl having 1 to 4 C atoms, i.e. methyl, ethyl, propyl, isopropyl, n-butyl, nibutyl, isobutyl, tertiary butyl, in which case a hydrogen atom is preferred.

85 in formula (1) is a hydrogen atom, an alkyl group, an aliphatic acyl group containing 2 to 8 C-atoms, a formyl group, a 4- to
Cycloalkylcarbonyl group having 7 C-atoms, methoxyalkylcarbonyl group having 3 to 7 C-atoms, optionally substituted by nitro, halogen, alkyl or alkoxy benzoyl group, alkoxycarbonyl group, benzyloxycarbonyl group,
phenoxycarbonyl group, alkylthiocarbonyl group,
NIN-dialkylcarbamoyl group, N-alkylcarbamoyl group, N-7 chloroalkylcarbamoyl group having 5 to 8 C-atoms in the cycloalkyl group, N-flufoxy N-furkylcarbamoyl group, nitro, halogen, alkyl, N-phenylcarbamoyl group optionally substituted by alkoxy or haloalkyl,
Alkylsulfonyl group, alkenylsulfonyl group containing 2 to 4 C atoms, halogenated alkylsulfonyl group, halogenated alkenylsulfonyl group containing 2 to 4 C atoms, N-alkylsulfamoyl group group, N,
N-dialkylsulfamoyl group, 2 to 5 in the acyl group
N-acyl-N-alkylsulfamoyl, N-alkyl-N-methoxycarbonylsulfamoyl, dialkoxyphosphoryl, dialkoxythiophosphoryl, containing 2 to 5 C atoms; -2 with atoms
-Halogenated alkanoyl group, acyloxyacetyl group having 2 to 4 C atoms in the acyl group, alkoxyoxalyl group, in this case hydrogen atoms, 2 to 4 carbon atoms,
Preference is given to aliphatic acyl radicals having 8 C-atoms and benzoyl radicals which may be substituted by hydrogen, halogen, alkyl or alkoxy. Particularly preferred is
These are a hydrogen atom, an acetyl group, and a benzoyl group.

R6 in formula (1) is in the ortho-, meta- or para-position and is a halogen atom, a hydroxy group, an alkyl group each having up to 4 carbon atoms, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an alkylthio group. , an alkylsulfinyl group or an alkylsulfonyl group, a nitro group, an amino group, in which case a halogen atom, particularly a fluorine atom or a chlorine atom, is preferred.

Alkyl groups for R6 and R6 and BS and R6
The alkyl and alkoxy groups in the radicals mentioned for can be unbranched or branched and have from 1 to 4 C-atoms, unless otherwise specified; That is, the alkyl group or alkoxy group includes a methyl group, an ethyl group,
n-propyl group, isopropyl group, le-butyl group, nibutyl group, isobutyl group, tert-butyl group, methoxy group,
Ethoxy group, n-propoxy group, isobutoxy group, n-
Suitable examples include butoxy, isobutoxy, sec-butoxy and tert-butoxy.

Examples of R5 are hydrogen atom, methyl group, ethyl group, acetyl group, propionyl group, butyryl group, valeryl group, formyl group, cyclopropylcarbonyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, methoxyacetyl group, 2-methoxypropionyl group. group, 3-methoxypropionyl group, benzoyl group, 3-nitrobenzoyl group, 2-10 lupenzoyl group, 4-methylbenzoyl group, 4-methoxybenzoyl group, methoxycarbonyl group,
Ethoxycarbonyl group, benzyloxycarbonyl group,
Phenoxycarbonyl group, methylthiocarbonyl group, ethylthiocarbonyl group, isopropylthiocarbonyl M
, N,N-dimethylcarbamoyl group, N-methylcarbamoyl group, N-cyclohexylcarbamoyl group, N-methoxy-N-methylcarbamoyl group, N-(4-nitrophenyl)-carbamoyl fi, N-(2-chlorophenyl Cucarbamoyl group, N-(3-methylphenyl)
-carbamoyl group, N-(3-methoxy7phenyl)-carbamoyl group, N-methylsulfamoyl group, N, N-
Dimethylsulfa7yl group, N,N-diethylsulfamofyl M, N-acetyl-N-methylsulfamoyl group, N-butyryl-N-ethylsulfamoyl group, N-
Methoxycarbonyl-N-methylsulfamoyl group, N
-isopropyl-N-methoxycarbonylsulfamoyl group, methylsulfonyl group, chloromethylsulfonyl group, trifluoromethylsulfonyl group, prop-2-en-ylsulfonyl fi% 2.3t3-trichloroprop-2-en-ylsulfonyl group, jetoxyphosphoryl group, jetoxythiophosphoryl group, chloroacetyl group, 2-bromopropionyl group, acetoxyacetyl group,
It is an ethoxyoxalyl group.

Examples of R60 include methyl group, ethyl group, propyl group, n
-butyl group, isopropyl group, nibutyl group, isobutyl group, tertiary butyl group, fluorine atom, chlorine atom, iodine atom,
Hydroxy group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, allyloxy group, prop-2-ynyloxy group, methylthio group, ethylthio group group, methylsulfinyl group, ethylsulfinyl group, nyl group, methylsulfonyl group, ethylsulfonyl group, nitro group, and amino group.

Salts of the compound of formula (1) include salts suitable for agricultural use, such as alkali metal salts, especially potassium or sodium salts,
alkaline earth metal salts, in particular calcium, magnesium or barium salts and manganese-1 copper-1 zinc or iron salts, as well as ammonium and phosphonium salts,
For example, alkylammonium, dialkylammonium, trialkyl or tetraalkylammonium salts, benzyltrialkylammonium! , triphenylphosphonium salt, trialkylsulfonium [X is trialkylsulfoxonium salt].

The herbicidal cyclohexenone derivative of formula (1) is a tricarbonyl compound represented by formula (■): [wherein R1, R2, R4, BS and R6 each have the above-mentioned meaning], Ammonium compound B30-NH,Y (However, R
3 can be obtained by reacting with the above compound (Y represents an anion).

The reaction is preferably carried out in a heterogeneous phase in an inert diluent.
It is carried out in the presence of a base at a temperature between 0.degree. C. and 80.degree. C. or between 0.degree. C. and the boiling point of the reaction mixture. Suitable bases are, for example, alkali metals or alkaline earth golds, especially sodium,
Carbonates, bicarbonates, acetates, alcoholades, hydroxides or oxides of potassium, magnesium and calcium. Further autobases such as pyridine or tertiary amines can also be used.

The reaction is within the pii range of 2 to 9, especially 4.5 to 5.
It progresses particularly well within the pg range of 5. Adjustment of the pH range is preferably carried out by adding an acetate, for example an alkali metal acetate, in particular sodium or potassium acetate, or a mixture of both salts. The alkali metal acetate is added in an amount of, for example, 0.5 to 2 mol at a temperature of 0.0° C. to the ammonium compound of the formula: R''0-NH5Y (wherein R3 and Y are as defined above).

as solvents or, for example, dimethyl sulfoxide, alcohols such as methanol, ethanol, isopropanol, penzole, optionally tetrachlorinated hydrocarbons,
For example, chloroform, dichloroethane, hexane, cyclohexane, esters such as ethyl acetate, ethers such as dioxane, tetrahydrofuran are suitable.

The reaction is complete after a few hours, and the reaction product is further removed by concentrating the mixture, adding water, extracting with a non-polar solvent such as methylene chloride, and distilling off the solvent under reduced pressure. Can be isolated.

Furthermore, the compound of formula (1) can be prepared by combining a tricarbonyl compound of formula CI with a hydroxylamine of the formula:
between 0° C. and the boiling point of the reaction mixture, especially from 15° C. in diluent.
1 can be obtained by reaction at temperatures between 70°C. Alternatively, the hydroxylamine can be used as an aqueous solution.

Suitable solvents for this reaction are, for example, alcohols such as methanol, ethanol, impropatol, cyclohexanol, optionally chlorinated hydrocarbons such as hexane, cyclohexane, methylene chloride, doluol, dichloroethane, esters, etc. acetic acid ethyl ester, nitriles such as acetonitrile, cyclic ethers such as tetrahydrofuran.

The alkali metal salt of the compound of formula (1) can be obtained by treating this compound with sodium hydroxide or potassium hydroxide in aqueous solution or in an organic solvent, for example methanol, ethanol, acetone. Sodium alcoholade and potassium alcoholade can also be used as bases.

Other metal salts, such as manganese salts, copper salts, zinc salts, iron salts,
Calcium salts, magnesium salts and barium salts are n)
It can be obtained from the IJ salt by reaction with the corresponding metal chloride in an aqueous solution. Ammonium salts, phosphonium salts, sulfonium salts and sulfoquinicum salts can be prepared by reacting the compound of formula (1) with ammonium hydroxide, phosphonium hydroxide, sulfonium hydroxide or sulfoxonium hydroxide, as the case may be. Alternatively, it can be obtained in an aqueous solution.

Novel tricarbonyl compounds of the formula CD) have the formula [wherein,
Cyclohexane-1,3-dione represented by Bl, 14, Hf+ and R6 are each as described above] by a method known in the literature ["Tetrabsdron Letters", Vol. 29, No. 2491 (1975)].

New compounds of formula Cm) are obtained in the acylation of compounds of formula (■), which may occur as isomeric mixtures and are rearranged in the presence of imidazole or pyridine derivatives (JP-A-54-63052). ) can also be prepared by an intermediate step of enol esters.

It is clear from the foregoing description that the new tricarbonyl compounds of formula (II) are used as important intermediates for the preparation of compounds of formula (1) with a herbicidal action.

The compound of formula (■) can be obtained by methods known in the literature, as is again evident from the following reaction scheme: cyclohexenone derivative of formula CI &); Carbonyl compound [However, in the above formula, Bl and R4 are hydrogen atoms, B2 is an alkyl group having 1 to 4 C-atoms, and R3 is an alkyl group having 1 to 4 C-atoms. groups, alkenyl groups with 3 or 4 C-atoms, 10genated alkenyl groups or probargyl groups with 3 or 4 C-atoms and 01-3)) , RB&! Aliphatic acyl groups having 2 to 8 C-atoms, formyl groups, cycloalkylcarbonyl groups having 4 to 7 C-atoms, methoxyalkylcarbonyl groups,
Nitro, norogen, alkylmodi< may be substituted with alkoxy, benzoyl group, alkoxycarbonyl group, benzyloxycarbonyl group, phenoxycarbonyl group, alkylthiocarbonyl group, N,N-dialkylcarbamoyl group, N-alkoxy-N-purkyl group Carbamoyl group, alkylsulfonyl group, alkenylsulfonyl group, halogenated alkylsulfonyl M, N-
furkylsulfamoylm, NxN-dialkylsulfamoyl group, N-acyl-N-alkylsulfamoyl group having 2 to 5 C atoms in the acyl group, N-alkyl-N-methoxycarbonylsulf Famoyl group, dialkoxyphosphoryl group, dialkoxythiophosphoryl group, 2-halogenated alkanoyl group, acryloxyacetyl group or alkoxyoxalyl group, RQX 7
6 represents an alkyl group, a norogen atom, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyl group, an oxy group, an alkylthio group, an alkylsulfinyl group, an alkylsulfonyl group, a nitro group, or an amino group.
] is a compound of the formula (Natsu&) or (I[) in which R+1 is a hydrogen atom, Rh is as above and Y is a leaving group, such as a chlorine atom, a bromine atom or a carboxylate group. can be obtained by reaction with an electrophile of the formula 2R''Y (in).

This reaction is optionally carried out in an inert organic solvent. Suitable ones include 9, for example hydrocarbons.

Examples: everigroin, benzine, doluol, pentane,
Cyclohexane; Acetonitrile, butyronitrile, benzonitrile, ethers such as diethyl ether, tetrahydrofuran, dioxane, esters such as ethyl acetate, methyl propionate/L
/, a ketone, such as acetone, methyl ethyl ketone, or an amide, such as N,N-dimethylformamide or formamide. It is also possible to use mixtures of these solvents. The amount of solvent is from 100 to 5000% by weight, based on the aniline derivative used, preferably in the presence of a conventional acid acceptor. Applicable are alkaline earth hydroxides, alkali metal carbonate rings, alkali metal hydrogen carbonates, alkaline earth metal aqueous products, alkaline earth gold carbonate rings, alkaline earth metal hydrogen carbonates, alkaline earth metals. Metal oxides or amines, such as sodium bicarbonate, potassium carbonate, triethylamine, tributylamine, pyridine, N,N-dimethylaniline, 'N,N-dimethyl-N-cyclohexylamine, quinoline. The amount of acid acceptor is 1 to 4 mol per mol of aniline derivative used.

The reaction temperature is between -20°C and +150°C, especially 20°C.
~80°C. Electrophile R5Y and Formula 1 (Ia)
The compounds used as the initiator composition (II) are preferably used in a 1 equimolar ratio.

Formula: 15Y (However, BS and Y represent the above)
Examples of compounds are carboxyl halides.

Carboxylic acid anhydride, chloroformate, alkylthiocarbonyl chloride, N,N-dialkylcarbamoyl chloride, N-alkoxy-N-alkylcarbamoyl chloride, N-alkylsul7amyl tetralide, N-
Acyl-N-alkylsul 7 amoyl chloride, for example of the formula: %Formula% [wherein R8 is an alkyl group having 1 to 7 C-atoms, a cycloalkyl group having 3 to 5 C-atoms, 2～
ife = A4 which may be substituted by a methoxyalkyl group having 4 C-atoms or by nitro, halogen, alkyl having 1 to 4 C-atoms or alkoxy having 1 to 3 C-atoms; Carboxylic acid halide represented by formula 1: Formyl acetate anhydride represented by formula 9: B90-00-01 [wherein R9 is an alkyl group having 1 to 4 C-atoms, a benzyl group or a phenyl group] A chloro-acid ester represented by the formula:

RIG S-00-01 Alkylthiocarbonyl chloride represented by the formula: [wherein BIG represents an alkyl group having 1 to 4 C-atoms], [wherein Bll and B10 represent 1 to 4 ○ atoms] N,N-dialkylaminocarbamoyl chloride represented by alkylthio having the formula: [wherein 113 is 1
Represents an alkyl group having ~4 〇 atoms B14
represents an alkoxy group having 1 to 4 〇 atoms]
N-alfoxy N-alkylcarbamoyl chloride, formula: % formula % [wherein R15 is an alkyl group having 1 to 4 〇 atoms, an alkenylsulfonyl group having 3 or 4 〇 atoms, represents a halogenated alkylsulfonyl group having up to 3 halogen atoms], a sulfonyl chloride represented by the formula: [wherein R16 represents an alkyl group having 1 to 4 〇 atoms, R17 represents a hydrogen atom, represents an alkyl group having 1 to 4 〇 atoms, an acyl group having 2 to 5 C-atoms, or a methoxycarbonyl group]; dialkoxyphosphoryl chloride and dialkoxythiophosphoryl chloride, each represented by an atom and 118° R19 represents an alkyl group having 1-4 ○ atoms;
Formula: [In the formula, FP and R2t represent a H atom or an alkyl group having 1 to 4 ○1 atoms, and Hal is a fluorine atom.

2-tetragenated alkanoyl chloride represented by the formula: [wherein R22 represents an alkyl group having 1 to 4 C-atoms] ] Acyloxyacetyl chloride is an alkoxyoxalyl chloride of the formula: [wherein R23 represents an alkyl group having 1 to 4 C-atoms].

Furthermore, a cyclohexenone derivative represented by the formula (Ic): and a tricarbonyl compound represented by the formula (It): [However, the above formula R1 and ? represents a hydrogen atom.

R2 represents an alkyl group having 1 to 4 C atoms.

R5 is an N-alkylcarbamoyl group, an N-cycloalkylcarbamoyl group having 5 to 8 atoms in the cycloalkyl group, or nido p, or a halogen.

Represents an N-7enylcarbamoyl group optionally substituted with alkyl or alkoxy.

P is an alkyl group, a halogen atom, or a hydroxy group.

represents an alkoxy group, an alkenyloxy group, an alkynyloxy group, an alkylthio group, an alkylsulfinyl group, an alkylsulfonyl group, a nitro group or an amino group. In R7, after the reaction, formulas (1) and (II
) represents a group that yields the corresponding group R5 in ). ``This reaction can optionally be carried out using catalysts 9 used for the isocyanate reaction, such as tertiary amines such as triethylamine, 1,4-diazadicyclo-4-[2,2,2)-octane, nitrogen-containing heterocyclic compounds 2 such as pyridine, 1,2
-dimethylimidazole□-, or an organotin compound 1, such as dibutyltin diacetate, dimethyltin dichloride, and optionally a solvent inert under the reaction conditions 9, such as a hydrocarbon 1, such as ligtetrain, benzine, Doluol, pentane, cyclohexane, halogenated hydrocarbons 1 such as cyclized methylene, chlorotetraform, dichloroethane, chlorobenzole, o-, m- or p-dichloropenzole, nitrated hydrocarbons 51EIN, tGf nitropenzole, Nitromethane, nitriles such as acetonitrile. Butyronitrile.

benzonitrile, ethers such as diethyl ether,
Tetrahydrofuran, dioxane, ester, vinegar E1
? ethyl esters, propionic acid methyl esters, ketones such as acetone, methyl ethyl ketone or amides,
For example, it is carried out in the presence of N,N-dimethylformamide or formamide [7-ben-Weyl (Hou
ben-Weyl)'s ``Methoden 6er org''
Anischen Ohemie)”, Volume 1.

Page 132, Georg Thieme
ieme.

Stuttgart, 4th edition, 1952].

The amount of catalyst is 0.1 to 0.1 to the aniline derivative used.
It is 5 mol%. The amount of solvent is 100-10000
Vary between % by weight. Reaction temperature is -20℃~+15℃
It can vary between 0°C, especially between 08°C and 100°C.

Catalytic hydrogenation of the nitro compound of formula (V) leads to the corresponding amino compound of formula (Ib) 9: nTJ In this case, for example, tetrahydrofuran, dioxane, C8-0. -Alcohol.

In the presence of an inert solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, N,IJ-dimethylformamide, pyridine, acetate, acetone, water or mixtures of these solvents,
Under pressure of 1-5 bar.

In particular, under normal pressure, at a temperature of 0°C to 80°C without adding a commonly used hydrogenation catalyst such as palladium, platinum, or nickel,
It is especially cultivated at room temperature.

The derivatives of formula (M) required to prepare compound V can be obtained by the divine method: (M) in this case the "dicarbonyl- or tricarbonyl step"
The point of entry of the nido tetragroup at t depends on t by controlling the substitution of the electrophilic aromatic compound in a critical manner. For example: 0 Hemorrhoid N Examples: Next, the production of the cyclohexene derivative of formula 9 (1) will be explained in detail with reference to examples.

Example 1 5.3 g of 2,-butyryl-(3-nitro-4-methoxyphenyl)-,cyclohexane-1,3-dione was dissolved in P67 charcoal (10%) in tetrahydrofuran 30011/.
Hydrogenation is carried out at 25° C. under normal pressure in the presence of 3 g. Hydrogen 0
．． After absorption of 91, the solution is dried over IJ sulfuric acid, filtered, added with 1.3 g of sodium bicarbonate and reacted with 1.2 g of a7tyl chloride. 16
After stirring for an hour, the reaction solution is filtered and concentrated.

The remaining oil is crystallized from diethyl ether and filtered with suction. 5-(3-acetylamino-4-methoxy-phenyl)-2-butyryl-3 with melting point 102°C to 106°C
-Hydroxy-Schiff-tetrahex-2-en-1-one 3g
(Yield 55%) is obtained.

Example 2 5-(3-acetylamino-4-methoxy-phenyl)
-2-butyryl-3-human tetraxycyclohexane 2-
3 g of en-1-one are stirred with 0.95 g of O-allylhydroxylamine hydrochloride and 0.8 g of sodium bicarbonate in 40 d of methanol for 16°. After concentration, methylene chloride is added to the reaction mixture, which is washed with water, dried and concentrated. The remaining residue is stirred with diisobrobyl ethyl and filtered. 5-(3-acetylamino-4-methoxy-phenyl)-2-(1-allyloxyiminobutyl)-3-hydroxy-cyclohex-2 with a melting point of 136°C to 137°C
2.0 g (57% yield) of -en-1-one are obtained (compound A 11 ).

Example 3 2-(1-ethoxyiminobutyl)-3- and do4xy-
To 4 g of 5-(3-amino-4-methoxy-7enyl)-cyclohex-2-en-1-one was added 1.3 g of methanesulfonyl chloride in pyridine 50rd at 25°C, and this was allowed to stand for 16 hours. Stir.

The reaction solution is placed on ice and brought to pH 1 with hydrochloric acid.

The reaction solution is extracted with methylene chloride, the organic phase is dried, concentrated and
-(1-ethoxyiminobutyl)-3-hydroxy-5
-(4-methoxy-3-methylsulfonamidophenyl)-cyclohex-2-en-1-one 3.6 g (
Yield 74%) is obtained (compound boiled 64).

Example 4 5-(3-amino-4-methoxyphenyl)-2-(1
4 g of -ethoxyiminobutyl)-3-hydroxy-cyclohex-2-en-1-one in 5 om of pyridine.
Stir for 16 hours at 5° C. with 2.2 g of jetoxythiophosphoryl chloride. The reaction solution is placed on ice and brought to pH 1 with hydrochloric acid.

The reaction solution is extracted with methylene chloride, filtered on silica gel, concentrated and 5-(3-jethoxythiophosphorylamino-4-methoxy-phenyl)-2-(1-ethoxyiminobutyl)-3- 4 g (yield 69%) of an oil consisting of hydroxy-cyclohex-2-en-1-one is obtained (compound 76).

Example 5 5-(3-aminobo,4-methoxyphenyl)-2-(
4 g of 1-ethoxyiminobutyl)-3-hydroxy-cyclohex-2-en-1-one in pyridine 50111
Methylaminosulfonyl chloride 1.5 at 25°C in 7
Stir with g for 16 hours. The reaction solution is placed on ice and brought to pH 1 with hydrochloric acid.

The reaction solution is extracted with methylene chloride, the organic phase is dried, concentrated and 2-(1-ethoxyiminobutyl)-3-hydroxy-5-(4-methoxy-3- 2.2 g of N-methyl-sul7-amoylamido)-cyclohex-2-en-1-one (yield 43%)
) is obtained (compound A75).

Example 6 31 g of 2-acetyl-3-hydroxy-5-(2-methoxyphenyl)-cyclohex-7-2-en-1-one was dissolved in 140 g of glacial acetic acid, and concentrated sulfuric acid was added to this solution while cooling at 25°C. 140- was added and 7.7 g of 98% nitric acid was rapidly added dropwise followed by stirring for 30 minutes.

It is then poured into an ice/methylene chloride mixture, the organic phase is separated off, washed with water and dried over sodium chloride. The dark oil obtained after concentration is filtered over silica gel in methylene chloride and concentrated. yellow crystal 27.5
g (yield 76%) was obtained.

It is 20% 2-acetyl-3-hydroxy-5-(
2-Me)xy-ethrophenyl)-cyclohex-7-
2-en-1-one (A), 80% 2-acetyl-3
-Hydroxy-5-(2-methoxy-5-nitrophenyl)-cyclohex-2-en-1-one (B), mixed melting point 145°G-151'C0 (A)
(B) 15 g of the above product mixture consisting of A and B (1:4) were combined with 4.2 g of sodium bicarbonate and 4.6 g of 0-ethylhydroxylammonium chloride in methanol at 1 ml.
Stir for 6 hours, concentrate, take up in methylene chloride, shake out with water, dry and concentrate.

This residue was triturated in diisopropyl ether.

and suction filtration. Additionally, 15.5 g of a 1:4 mixture of the corresponding 0-ethyloxime ethers 0 and D (yield 91
%) is obtained. Mixed melting point 132°C to 142°C.

Product mixture 0: D=l: 410.3 g are hydrogenated in 500 m/ml of tetrahydrofuran in the presence of 3 g of palladium on charcoal (10%) at 25° C. under normal pressure. After uptake of hydrogen 31, the mixture is dried over sodium sulfate, filtered and concentrated. Corresponding anilines E and F
A quantitative yield of 9.5 g of an oily 1:4 mixture of .

(E) (F) 9 g of this aniline mixture was added to 50 ml of tetrahydrofuran.
2.4 g of sodium bicarbonate are added to this solution, which is reacted with 2.2 g of acetyl chloride while stirring. After stirring for 16 hours, the reaction solution was filtered with suction.
Concentrate and chromatograph the remaining oil on silica gel using acetic ester. 5 pure isomers
-(3-acetamido-2-methoxyphenyl)-2-
(1-ethoxyiminoethyl)-3-hydroxy-cyclohex-2-en-1-one 0.9 g (yield 9%)
).

and the pure isomer 5-(5-acetamido-2-methoxyphenyl)-2-(1-ethoxyiminoethyl)-
3-Hydroxy-Schifftetrahex-2-2-1-one 3
．． 6 g (35% yield).

is obtained.

Example 7 5-(2-fluorophenyl)-Schiftetrahexane-1.
60 g of 3-dione was dissolved in 500 ml of concentrated sulfuric acid at -20°C, and this solution was dissolved in 18.3 g of 98% nitric acid at -20°C.
2) to o in 60 minutes. This reaction mixture was poured into 5 liters of ice water.
Stir and mix into the mixture. The precipitated crystals are filtered off with suction and dried. 5-(2-Fluoro-5-nitrophenyl)-cyclohexane-1.3- with a melting point of 171'C to 173C
60.5 g (83% yield) of dione are obtained.

5-(2-Fluoro-5-nitrophenyl)-cyclohexane-1,3-dione 54ge was dissolved in 500 g of cyclized methylene, 18.7 g of pyridine was added to this solution, and this was dissolved in chlorobutyric acid at room temperature for 1 hour. O-acylated with 25.2 g. After stirring for 16 hours, the reaction solution is shaken out with ice water, shaken out with 5% sodium bicarbonate solution, shaken out again with ice water, dried over sodium sulfate and concentrated. The remaining oil is taken up in about 50 ml of acetic acid ester and left for 5 days with 3 g of 4-dimethylaminopyridine. This organic phase was shaken out twice with 5% hydrochloric acid, dried,
and concentrate. The remaining residue is recrystallized from Improper Tools. 2-Butyryl-5-(2-
Fluoro-5-nitrophenyl)-3-hydroxy-cyclohex-2-en-1-one 33 g (yield 48%)
is obtained.

2-Butyryl-5-(2-fluoro-5-nitrophenyl)-3-hydroxy-cyclohex-2-en-1-
25 g of on, 7.4 g of sodium bicarbonate and 0-
8.6 g of ethylhydroxylammonium chloride are stirred in 100 methanol for 16 hours, concentrated, taken up in methylene chloride, washed with water, dried and concentrated again. 24 g (84% yield) of 2-(1-ethoxyiminobutyl)-5-(2-fluoro-5-nitrophenyl)-3-hydroxy-cyclohex-2-en-1-one as a viscous oil. can get.

23 g of this oil are hydrogenated in 500 ml of tetrahydro7ran in the presence of 5 g of palladium on charcoal (10%) at 25° C. under normal pressure. After absorption of hydrogen 4.51.

The oil is dried, filtered with suction and concentrated. 5-(5
-amino-2-fluorophenyl)-2-(1-ethoxyiminobutyl)-3-hydroxy-cyclohexe-2
19.6 g (93% yield) of -en-1-one are obtained as a viscous oil.

5.5 g of this oil are left to stand for 4 days at room temperature with 1 g of methyl isocyanate and 1 drop of dibutyltin diacetate in 50 ml of tetrahydrofuran.

After concentration, the residue is stirred with ether and dried. 2-(1-Ethoxyiminobutyl)-5-(2-fluoro-5-(3-methylureido)-phenyl]-3-hydroxy-cyclohex-2-en-1-one with melting point 120°CN122°C4. 4 g (yield 69%)
is obtained (compound &116).

Correspondingly, the following cyclohexenone derivatives of formula (I) are obtained: lI Kan Tadashi Tadashi Kawa Koro Fuchi Kan
Kangami lo mi country mi kan engineering river 鴴 閑mi 閤0l
-ICI211) groan n to e-
ωt's 0)l-IF4+-11-IPIFIH
F-11-1110I10 閤国 1) 閴 1) 川 川 川 川 川 川 閤 国 閤 み 工
1)
1) Kawa Kan Ta Misaki 01+ Kawa Kan Kan Work 0 Kan 1)
It's quiet, it's quiet, it's quiet, it's quiet, it's quiet, it's quiet
country ■ 1) country of the country ■
OS ~ υ Dimensions dimension Dimensions Dimensions or v
Place river quiet place quiet
To 010 F-1 □
11') 10M) 11') 11') 10 4010
101010 Kan Fuchi Kokuni Kawa Kan Kokumi Kan Kan Kokuni Kan? δ 〇０ 工 工 agon river kan oma 鵴斑 国 国 閑 閤 閑 閑 閑 閑 閑 海 Ｇａｎ Ｇａｎ Ｇａｒｄ Ｇａｎ ｄｅｎ
lIl+ 工 連 匡 閑 工 工 塡匡匡 閤 国 閑 閑 鴴 閤 位 m
Construction work opening river calm river 1) Dry construction work construction cursed country! lI2
Threshold kan kan threshold 閤 閤 閑 閑GaI
Opening of the country 1) 1) +1lll
Kan Kan Kan Kan Kan Work Kan Kan Mi River Flash Kan Place Threshold Kan Mi Kan Kan Kaku +1I18
engineering 1) country
Kan Kang Kan Kang Kang Country Industrial Crab Space Kan Mi Kaku
Placement work 1) Work ヱ mie @ t'-(
Oolo r4 CV IQ dimension t1'
) o o lo o o d I-I -
I-IS H〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜〜
〜〜〜〜ε ガδ 閤 A quiet night is a breeze,,,'S γ ′
) Masada 1) 1) Masada 1) 1) Country 1) 工 匡 工き田δ 閑 ヱ 閑 工 鴴 閑 閑 工
閤 gu 国国 喴 閤 閴 閤
Proverbs Country♂ Cvcv C1l N ~ to
~ To kankan kan 01+0II0II Tadashi - Abyss
閤 工 工 閤 = 1) ■ 1) Kan Sen 閑 閤 国 悶 工 Private 工 閤 匡 国Gaδ GAδ 1) 匡 閑 喑 田閤 1) 工 1) 閤 MI 1) True 庡 喑 喑 閑 工 国Kojin Koi Advanced Equipment 1) Standing
麴閤麴凰 瑑川国工
Kaikai Kan 1) River Kan Tadashi Ekan Country 1) Engineering Kan Ekuni Country Sakan Engineering 1) Country Engineering Exploration Field 1)
1 The cyclohexenone derivative of formula (I) has unique IH-nuclear magnetic resonance spectra data (chemical shift at δ value (ppm) in 0 DOIs, For tetramethylsilane as internal standard; 8 = - doublet, a = doublet,
q - quartet, m = multiplet) can be shown: Compound square characteristic signal 76 1, o (t, 3H); 3.9 (8, 3
H); 4.0-4.4 (m.

6H)? '7 1.0 (t, 3H): 3.85 (s
, 3H): 4.0-4.3 (m, 6H) 91 2.2 (8, 3H); 2.45 (II,
3H); 3.75 (8,3H); 6.95 (d,
LH); 7.15(t, LH); 8.20((1
,LH)95 2.2(s, 3H); 2.4
(s, 3H); 3.8(s, 3H); 6, s(d
, la); q, 45 (a, IH) 1 os
o, 9a(t, 3H); 4.1((1,2H);
6.55 (a, LH); 6.75 (s, LH);
7.10 (d, LH) 113 1.3 (t, 3
H); 6.4-6.6 (m), 6.85 (t) 13
6 3.6(s); 3.8(s); 6.5-6
．． 8 (m) 1'77 2.95 (t); 6.8 (
d); 7. j25 (m); 7.45 (m), 8.
35(s) 195 2.15(8); 3.4(11); 8
．． 1(8); 6.9-7.1(m); 7+85(d
) 218 o, 9r+(t); 1.3(t):
4.05-4.2(q)240 2.95(t
); 3.35 (m); 3.8 (s); 4.
15(q) 249 o, 95(t); 4.
1 ((1); [:4.75(q)i]6.7(8)
; 7.4(d) 308 g, 97(t); 4.12(q
); w, a6(d).

Cyclohexeno/derivatives of formula I and salts thereof.

For example directly sprayable solutions, powders, F! Turbid liquid.

Furthermore, in the form of highly concentrated aqueous, oily or other 9g liquids or dispersions, emulsions/oil dispersions, pastes, dusts, dusting agents or granules by spraying, misting, dusting, scattering or injection methods. Can be applied. The form of application is determined entirely by the intended use; in each case it is to be ensured that the irritating substances of the invention are as finely divided as possible.

To produce directly splashable solutions, emulsions, pastes or oil dispersions, mineral oil fractions of medium to high boiling point, such as melt oils or diesel oils, as well as feeder oils, as well as vegetable or animal products, can be used. source oils, aliphatic, annular and aromatic hydrocarbons such as penzole, doluol, xyl-11-ol,
paraffin.

Gutrahitol, phthalin, alkyl-substituted phthalin or derivatives thereof, such as methanol, ethanol, zo[
``Panol, buta/-l, ri[I form, tetracyclic carbonffi, cyclohexanol, cyclohexanone, ri[norpenzole, isofluoro 07, etc.].

Strong M agents such as N,N-dimedylformamide, shimedylsulfoxide, N-medylpy+1 lydone and water are used.

Aqueous use forms can be prepared from emulsions, pastes or wettable powders (spray powders), oil dispersions by addition of water. To produce emulsions, pastes or uradispersions 11k, the substances can be homogeneously mixed in water with wetting agents, adhesives, dispersants or emulsifiers, either as such or dissolved in oil or solvents. . Moreover, the effective substance
A concentrate consisting of a wetting agent, wetting agent, dispersing agent or emulsifying agent and optionally a solvent or liquid may be prepared, which is then added dropwise to dilution with water.

Surface-active substances include: lignin sulfonic acid, naphthalene sulfonic acid, alkali salts of phenolsulfonic acid, alkaline earth salts, ammonium salts, alkylaryl sulfonates, alkyl sulfonates, Alkyl sulfonates, alkali salts and alkaline earth salts of dibdelnaphthalene sulfonic acid, lauryl kneepool sulfate, fatty alcohol sulfate, fatty acid alkali salts and alkali-1 groups, sulfation to ↑, sadecanol, hepta Decanol, salts of octadecanol, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene or naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acid with phenol and formaldehyde, Polyoxyethylene-octylphenol needle, ethoxylated inoctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tribudylphenyl polyglycol ether, alkylaryl polyether alcohol, intridecyl alcohol, fatty alcohol ethylene oxide complex, ethoxyl castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acecool, sorbitol ester.

Lignin, sulfite waste liquor and methyl cellulose.

Powders, dusting powders and sprinkles can be prepared by mixing or milling together the active substance and a solid carrier material.

Coatings, such as coatings and homogeneous particles, can be made by binding the self-effect material to a solid carrier material. Solid carrier substances are, for example, minerals, such as silica gel, silicic acid, silicate gel, silicates, talc, carrion, atakure 1 limestone 2 lime, white J, f4 lumpy soil 9 calcareous yellow dead earth, clay, dolomite, diatomite , calcium sulphate, magnesium sulphate, magnesium oxide, ground synthetic resins, fertilizers such as ammonium halisulphate, ammonium phosphate, ammonium nitrate, urea and vegetable products such as cereal flour, bark, wood and walnut shell flour, cellulose powder and other solids. carrier material.

Examples of formulations are as follows.

When 1.90 parts by weight of compound 1 are mixed with N-methyl-α-pi(1 lido/10 parts by weight) a solution is obtained which is suitable for use in the form of very small drops.

11.20Lr+' part tv compound 7 wo, +-shi+
j-le 80 j Ti part 1 ethylene oxide 8 to 10
10 parts by weight of an additive product obtained by adding 1 mole of olei/acid-N-monoether/-ruamide, 5 parts by weight of a calcium salt of dodecylbenzole sulfonic acid, and 40 moles of ethylene oxide to 1 mole of castor castor. Dissolved in a mixture consisting of 5 parts by weight. Add this solution to 100% water
By injecting 000 parts by weight and subdividing into parts, a hydraulic dispersion containing 0.02% by weight of the active ingredient is obtained.

111.20 parts by weight of compound 3 was added to cyclohexanone 4
0 parts by weight, 30 parts by weight of isobutanol, 20 parts by weight of an additive product obtained by adding 7 moles of ethylene oxide to 1 mole of inoctylph, and 10 parts by weight of an additive product obtained by adding 40 moles of ethylene oxide to 1 mole of Castor. dissolve in This solution was injected into a 100,000 weight layer of water (1), and the active ingredient (1) was finely distributed.
, 02% by weight is obtained.

(2) Add 20 parts by weight of compound 111 to 25 parts by weight of N.J. hexanol, mineral oil fraction 6 with a boiling point of 210 to 280°C.
5 parts by weight and 40 moles of ethylene oxide are dissolved in a mixture consisting of 11 parts L of the additive product 11R1 and 1 mole of castor porridge. By injecting this solution into 100,000 parts of water and finely distributing it, the self-effective ingredients are 0.02% by gravity.
An aqueous dispersion containing f is obtained.

V, 20fTjJ1j part (D compound 7, 7
]-1-) Three parts of Lr-naphthalene-alpha-sulfonic acid lithium salt, 1 part of sodium chloride/acid from sulfurous waste liquid, 17 parts by weight of salt and 60 parts by weight of powdered silicic acid gel are thoroughly mixed. and milled in a Huffmer mill. By subdividing this mixture into 20,000 parts of water, a spray solution containing 0,0 m:tt% of the active ingredients is obtained.

411 parts of compound 33 in 3 parts is intimately mixed with 97 parts of fine Cl2-like kaolin. In this way, a 111'1 spray containing 3 mounds of effective substances and 1% of j% is obtained.

■ 30 mounds (1: part of Compound 56 was blown onto the powder 41, f1 acid gel 02 ton x 111 parts, and the surface of this silicic acid gel -1) and a mixture consisting of 8 parts of Bashifinura 8 parts h 11 parts were mixed tightly. Konwa. In this way, a preparation of a self-effective drug containing PI with good properties is obtained.

■ 20 parts of Compound 111 were mixed with 1 part of calcium N 2 tl'i of dibenzole sulfuric acid + 1 part of alcohol polyglycol ether 8 parts, and
, 2 parts of sodium salt of mer sulfofic acid-urinary acid lumaldehyde condensate and 68 parts of paraffinic mineral oil.
Mix intimately with parts by weight. A stable Urashe dispersion is obtained.

Xl, 10 parts by weight of compound 289, quizyrol gOi
, Ii: 7 nilf of the fR part and 8 moles of ethylene oxide. The mixture is mixed with 7 parts of the additive product added to 1 mole of Nyl. A solution containing 10% by weight of active substance is thus obtained.

Spraying can be carried out by pre-emergence treatment or post-emergence treatment. If the active substance is poorly tolerated by certain cultivated plants when using post-emergence treatment methods,
Using a sprayer with herbicide.

Use a spraying technique that minimizes contact with the foliage of sensitive plants and allows the active substance to reach the foliage of undesirable plants growing underneath or on exposed soil surfaces. You can also do it [Bost-Dilefted (
post-directed) method.

lay-by method].

The amount of active substance used is 0.025-3 kg/ha, especially 0.06 kg/ha, depending on the season, target plant and growth stage.
~0.5 kg/ha.

The effect of the cyclohexenone derivatives of the formula (1) on plant growth can be demonstrated by greenhouse tests: the test vessel was loam sand with an internal volume of 300 - and about 1.5% humus as substrate. Use a plastic pot with. Seeds of test plants are sown separately and shallowly according to type. In the case of pre-emergence treatment methods, the active substance is applied directly onto the soil surface. In this case, the active substance is suspended or emulsified in water as a dispensing agent;
and spray using a fine distribution nozzle. How much is used?

3.0 kg/ha.

After spraying the chemical, add a little water to the container to initiate germination and growth. The container is then covered with a clear plastic cap until # the material grows. This covering results in uniform germination of the test plants, as long as this is not impaired by the active substance.

To use the post-emergence treatment method, the test plants are grown to a growth height of 3 to 15 C11, depending on the growth form, and then treated. Dice are grown in a substrate with increased peat fines (beet) content. For post-emergence treatment methods, sow directly.

Either plants are selected from plants grown in the same container, or plants are first grown separately as cotyledons and transplanted into test containers a few days before treatment. The usage amount for the post-emergence treatment method is 0.06-0.5 kg/ha of active substance.

Covering is not required with the 9 post-emergence treatment method.

The test container is set up in a greenhouse, where tropical plant species are
A hot range (20°C to 35°C) is preferred.

For temperate plant species, the temperature is preferably 10°C to 25°C.

The testing time ranges from 2 to 4 weeks. During this time, the plants are grown and their response to the 9 individual treatments is evaluated. 0-1
Evaluation is made on a scale of 00. in this case.

100 means no plant growth or complete destruction of at least the soil surface.

The plants used in greenhouse trials consist of the following species;
myosuroides),
Avena fatua (oat), Avena 5ativ
a) (x Nbaku), Eki/Croa Tarsugari (
Echinochloa crus-galli)
(Hie), Glycine Max (G4ycinemax)
') (Dice), Lolium Multi 70 Lum (Lo
lium multiflorum) (Hosomugi),
Oryza sativa (Oryza 5ativa) (rice), Setaria italica (5etaria 1tal)
iaa ) (Awa), Cinnabis alba (5inPLp
is alba ) (mustard), Sorghum halepenae (sorghum).

When using pre-emergence treatment methods 1. For example, compounds Al, 7.
．． '33.56 was found to have a herbicidal effect on plants from the Poaceae treetops, and Cinnabis alpa (5
inapis alba) remains completely undamaged as a representative example of bichiba treetops.

In the case of post-germination treatment method 1 For example, compound dust 56 and 114
and A'109 and Ill are active substances 0.06
kg/ha shows a strong herbicidal action against illustratively selected grasses, and the dice are not damaged as dicotyledonous cultivated plants. The compounds 7 and 9 are suitable, for example, for controlling barnyard grass in rice.

Undesirable grasses are already used sparingly! can be controlled using, for example, compound 109 or Ill, and dicot remains unaffected as an example of a dicotyledonous cultivated plant.

With the two illustratively selected compounds/Ffli 60, 64 and 75, undesirable grasses in the cultivated plants can be well controlled if the tolerability to Dice is good.

In exactly the same way, 9, for example compounds 416 and 91, are also suitable for controlling a broad spectrum of undesirable grasses, in which case soybean is not damaged in any way as a cultivated plant.

A high level of action against undesirable plants from grasses is shown by 1, for example compound 103. However, it does not cause any damage in wheat.

Undesirable grasses can be successfully controlled using one exemplary selected compound A 117 , 126 and 127. In this case, the Alfalfa palm as a cultivated plant is not damaged at all.

For controlling important weeds in rice, 1, for example Compound Ya 289, is suitable. In this case, the compounds cause only minimal damage to cultivated plants.

Detectable spectrum of action for weed control.

In view of the tolerability to cultivated plants or undesirable effects on the growth of cultivated plants, as well as in view of the diversity of application methods, the compounds according to the invention can be used in a large number of cultivated plants. For example, the following cultivated plants apply: Onion (^l1iulIcepa) Pirylapur (^nanas cosusus) Lean-ton bean (Arachis hypogaea) Asparagus (Hasparagus official)
is) Chard (l1eta vulgaris s)
pp, altissi*a) Humpback Shisha (l1cta
vulgaris spp, rapa) Anonobu/゛sui (llcta vulgaris spp, esc
ulenta) Brush power napas (variant napas) (1lrassica napLls Qar, nap
us) Brush force Navas (variety Nabo Brasica) (l
1rassica napus var, napobr
assica) Brush force Rebus (variant mule) (1lrassica napus var, rapa
) Brezihorn Navas (var. Sylvestris) (1l
rassica apus var, 5Nvestri
s) Camellia 5inensis
) Benibari (CarthaIlus tinctor)
ius) Carrier Ilinoinensis (Carya ; 1linoinensis) Marbushukan (Cttrusales man) Grapefruit (
Citrus ++axima) Daidai (C1tru
s reticulata）zu-tsu mika :/
(Citrus 5inensis) Coffee arabica (Coffeac
anephora, Corfea Nbarica)
) Cucumis gqla Cucumber (
Cucuiis 5aLivus)
nodon dactylon) carrot 7 (1) au
cus carota) Abushami (Elaeis g.
uiccnis) Strawberry (Pragaria vcs)
ca) person -7, (GlycinCwax) tree + hanging (Gossypium l100r8; uLuI
Il (Gossypium.

arborcum1Gossypiu+lhcrbac
auIllsGossypiuw vitifoliu
m) ) Sunflower (lIC1ianLhus annu
us) Jerusalem artichoke (1IclianLhus Lubcr)
osus) Rubber Tsuki (l1avca brasi l
1ensis) human skin (llordaum vulga)
ra) Ilumulus 1upul
us) American potato (lpomoca bata'ta)
s) Juglans regia latch; 1. ca zadiva (1, actuca 5aliva)
) Lentil (1, cns culinaris) flax (1, tnuIlus; tatissiiul)
Mato (Lycopcrs; con Iyco
persicum) Malus spp,
) 1-Manihot esculent
a) Muraza; Mcdicago 5at
iva) Mentha piperita M'usa spp, ) Tobacco 1 (N1 cotiana tabacu++ (
N, rustica) ) Olive (0lca euro)
opaaa) Rice (0ryza 5ativa) Millet (Pan1cc+m 1 mouth iiceum) Azuki (
1'haseolus! unatus) the hatred game (1'
hascolus 1llu'ngo);tgazzaza'
t” (Phaseolus vulgaris) Parsley (PcnnisCtuIlglaucum) Beto [1
Cerium crispum (1'aLrosclinum crispum)
spp, tubcrosum) Toinhi (+'1cca
abtcs) Fir (Abiesalba) Mano%4 (1'1nus spp,) Shi11;
unus avium) Anse (Prunus dowestica) Prunus dulcis (f'runus dulc;s) Peach (r
'runus pcrsica) pear (Pyrus c
Robes 5ylvest
rc) Hawthorn (Rtbes tlVa-crispa)
) Castor bean (Ricinus communis) Sugarcane (Saccharuw off icinaru)
m) Rye (5ecale ccreale) rubber (
Sesamum indicum) Potato (Sol
anuw tuberosum) mo(J j shi(Sor)
ghum bicolor (s, vulgare)
) 'Sorghum, de sojnas
dochna) spinach (5 pinacia o
lcracea) Cacaoki (Theobroma c)
acao) Purple Somexa (Trifol+um p
wheat (Triticum aesti)
vum).

Vaco+nium corymbosu
m) Vacciniu* vitis-1d
aea) Vicia faba Vigna cine/cis (variety/guiculata) (Vi
gna s+nensis (V, unguicula
ta)) Grape (Vitis vinHera) Maize CT Koshi (Zaa llays) In order to widen the spectrum of action and to achieve a synergistic effect, the cyclohexenone derivatives of formula (I) and their salts can be used with other herbicidal or growth-promoting agents. It can be mixed with and commonly distributed with numerous representatives of the group of active substances with a regulating effect. For example, mixed components include diazine, 4H-,3,1-benzoxazine derivatives, benzothiadiazinone, 2,6-dinitopaniline, H-phenyl carbamate, thiol carbamate, helogenated carboxylic acid, triazine, amide. , urea, diphenyl ether.

Doriazinone, uracil, benzofuran derivatives.

This includes quinolinecarboxylic acid derivatives and other herbicidal active substances.

'Furthermore, the compound of formula (1) may be applied alone or in combination with other herbicides, and furthermore, other complementary protection agents.

For example, it may be useful to mix and spray them with agents for controlling pests or phytopathogenic fungi or bacteria. A further important consideration is the miscibility with the mineral salt solutions used to eliminate nutritional deficiencies and minor constituent deficiencies. It is also possible to add non-phytotoxic oils and concentrated oils.

Claims (11)

[Claims] (1) Formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^1 represents a hydrogen atom, a methoxycarbonyl group, an ethoxycarbonyl group, a methyl group, or a cyano group, and R^ 2 represents an alkyl group with 1 to 4 C-atoms, R^3 is an alkyl group with 1 to 4 C-atoms, an alkenyl group with 3 or 4 C-atoms, 3 or 4 R^4 represents a hydrogen atom or an alkyl group having 1 to 4 C-atoms; 5 is a hydrogen atom, an alkyl group, an aliphatic acyl group having 2 to 8 C-atoms, a formyl group, a cycloalkylcarbonyl group having 4 to 7 C-atoms, a methoxyalkylcarbonyl group, nitro, halogen, Benzoyl, alkoxycarbonyl, benzyloxycarbonyl, phenoxycarbonyl, alkylthiocarbonyl, N,N-dialkylcarbamoyl, N-alkylcarbamoyl, cycloalkyl optionally substituted with alkyl, alkoxy or haloalkyl N-cycloalkylcarbamoyl, N-alkoxy-N-alkylcarbamoyl, N-phenylcarbamoyl optionally substituted by nitro, halogen, alkyl or alkoxy, having 5 to 8 C-atoms in the radical group, alkylsulfonyl group, alkenylsulfonyl group, halogenated alkylsulfonyl group, N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group,
N-acyl- having 2 to 5 C-atoms in the acyl group
N-alkylsulfamoyl group, N-alkyl-N-methoxycarbonylsulfamoyl group, dialkoxyphosphoryl group, dialkoxythiophosphoryl group, 2-halogenated alkanoyl group, acyloxyacetyl group or alkoxyoxalyl group, R ^6 represents an alkyl group, a halogen atom, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkylthio group, an alkylsulfinyl group, an alkylsulfonyl group, a nitro group, or an amino group] and salts of this compound. (2) Claim 1 in which R^1 represents a hydrogen atom
Compounds described in Section. (3) Claim 1, in which R^1 and R^4 represent a hydrogen atom, R^5 represents a hydrogen atom, an acetyl group, or a benzoyl group, and R^6 represents a fluorine atom or a chlorine atom. Compounds described in Section. (4) Formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^1 represents a hydrogen atom, a methoxycarbonyl group, an ethoxycarbonyl group, a methyl group, or a cyano group, and R^ 2 represents an alkyl group with 1 to 4 C-atoms, R^3 is an alkyl group with 1 to 4 C-atoms, an alkenyl group with 3 or 4 C-atoms, 3 or 4 R^4 represents a hydrogen atom or an alkyl group having 1 to 4 C-atoms; 5 is a hydrogen atom, an alkyl group, an aliphatic acyl group having 2 to 8 C-atoms, a formyl group, a cycloalkylcarbonyl group having 4 to 7 C-atoms, a methoxyalkylcarbonyl group, nitro, halogen, Benzoyl, alkoxycarbonyl, benzyloxycarbonyl, phenoxycarbonyl, alkylthiocarbonyl, N,N-dialkylcarbamoyl, N-alkylcarbamoyl, cycloalkyl optionally substituted with alkyl, alkoxy or haloalkyl N-cycloalkylcarbamoyl, N-alkoxy-N-alkylcarbamoyl, N-phenylcarbamoyl optionally substituted by nitro, halogen, alkyl or alkoxy, having 5 to 8 C-atoms in the radical group, alkylsulfonyl group, alkenylsulfonyl group, halogenated alkylsulfonyl group, N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group,
N-acyl- having 2 to 5 C-atoms in the acyl group
N-alkylsulfamoyl group, N-alkyl-N-methoxycarbonylsulfamoyl group, dialkoxyphosphoryl group, dialkoxythiophosphoryl group, 2-halogenated alkanoyl group, acyloxyacetyl group or alkoxyoxalyl group, R ^6 represents an alkyl group, a halogen atom, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkylthio group, an alkylsulfinyl group, an alkylsulfonyl group, a nitro group, or an amino group] and salts of this compound. In the manufacturing method, formula (II)
: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) Tricarbonyl represented by [In the formula, R^1, R^2, R^4, R^5 and R^6 each represent the above] a) with an ammonium compound of the formula: R^3O-NH_3Y, where R^3 represents the above and Y represents an anion, optionally in an inert diluent. Therefore, the reaction may be carried out in the presence of water at a temperature of 0°C to 80°C in the presence of a base, or b) represented by the formula: R^3O-NH_2 [wherein R^3 represents the above]. A process for the preparation of cyclohexenone derivatives of the formula (I), characterized in that they are reacted with hydroxylamine, optionally present in an aqueous solution, in an inert solvent. (5) Formula (Ia): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(Ia) [In the formula, R^1 and R^4 represent hydrogen atoms, and R^2 represents 1 to 4 C - represents an alkyl group having 1 to 4 C-atoms, an alkenyl group having 3 or 4 C-atoms, 3 or 4 C-atoms and 1 to 4 C-atoms; represents a halogenated alkenyl group or propargyl group having 3 halogen substituents, R^5 is an alkyl group, an aliphatic acyl group having 2 to 8 C-atoms, having 4 to 7 C-atoms cycloalkylcarbonyl group, methoxyalkylcarbonyl group, benzoyl group optionally substituted with nitro, halogen, alkyl, alkoxy or haloalkyl group, alkoxycarbonyl group, benzyloxycarbonyl group,
phenoxycarbonyl group, alkylthiocarbonyl group,
N,N-dialkylcarbamoyl group, N-alkylcarbamoyl group, N-cycloalkylcarbamoyl group having 5 to 8 C-atoms in the cycloalkyl group, N-alkoxy-N-alkylcarbamoyl group, nitro, halogen, N-phenylcarbamoyl group optionally substituted with alkyl or alkoxy, alkylsulfonyl group, alkenylsulfonyl group, halogenated alkylsulfonyl group, N-alkylsulfamoyl group, N,N
- dialkylsulfamoyl group, N-acyl-N-alkylsulfamoyl group having 2 to 5 C-atoms in the acyl group, N-alkyl-N-methoxycarbonylsulfamoyl group, dialkoxyphosphoryl group , dialkoxythiophosphoryl group, 2-halogenated alkanoyl group,
represents an acyloxyacetyl group or an alkoxyoxalyl group, and R^6 represents an alkyl group, a halogen atom, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkylthio group, an alkylsulfinyl group, an alkylsulfonyl group, a nitro group, or an amino group. In the method for producing cyclohexenone derivatives shown, formula (I): ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^5 represents a hydrogen atom, R^1, R^2,
R^3, R^4 and R^6 each represent the above] in a system optionally buffered to a certain pH value, optionally in the presence of an acid binder. -20℃~+1
At a temperature of 50° C., it is reacted with a compound of formula (III): IV): R^7-NCO(IV) [wherein R^7 is an alkyl group having 1 to 4 C-atoms, 5 to
a phenyl group optionally substituted by a cycloalkyl group having 8 C-atoms, nitro, halogen, alkyl having 1 to 4 C-atoms or alkoxy having 1 to 4 C-atoms; isocyanate represented by the formula (I a)
A method for producing a cyclohexenone derivative. (6) Formula (I b): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I b) [In the formula, R^1 represents a hydrogen atom, a methoxycarbonyl group, an ethoxycarbonyl group, a methyl group, or a cyano group, R^2 represents an alkyl group having 1 to 4 C-atoms, R^3 represents an alkyl group having 1 to 4 C-atoms, R^6 represents an alkyl group, a halogen atom, a hydroxy group , represents an alkoxy group, an alkenyloxy group, an alkylthio group, an alkylsulfinyl group, an alkylsulfonyl group, a nitro group or an amino group], the method for producing a cyclohexenone derivative represented by the formula (V): ▲ Numerical formula, chemical formula, table, etc. ▼(V) [In the formula, R^1, R^2, R^3 and R^6 each represent the above] The compound represented by hydrogen atom,
from 0°C in the presence of a hydrogenation catalyst, optionally under pressure and in the presence of an inert solution, optionally with the addition of a base.
A process for producing a cyclohexenone derivative of formula (Ib), which is characterized in that it is converted into an amino compound by reduction at a temperature of 80° C. by a method known per se. (7) Formula (IIa): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (IIa) [In the formula, R^2 represents an alkyl group having 1 to 4 C-atoms, and R^1 is a hydrogen atom , alkyl, aliphatic acyl with 2 to 8 C-atoms, formyl, cycloalkylcarbonyl with 4 to 7 C-atoms, methoxyalkylcarbonyl, nitro, halogen, alkyl, alkoxy or benzoyl group, alkoxycarbonyl group, benzyloxycarbonyl group, phenoxycarbonyl group, alkylthiocarbonyl group, N,N-dialkylcarbamoyl group, N-alkylcarbamoyl group, cycloalkyl group which may be substituted with haloalkyl. N-cycloalkylcarbamoyl, N-alkoxy-N-alkylcarbamoyl, N-phenylcarbamoyl optionally substituted by nitro, halogen, alkyl or alkoxy, alkylsulfonyl having ~8 C-atoms group, alkenylsulfonyl group, halogenated alkylsulfonyl group, N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group,
N-acyl- having 2 to 5 C-atoms in the acyl group
N-alkylsulfamoyl group, N-alkyl-N-methoxycarbonylsulfamoyl group, dialkoxyphosphoryl group, dialkoxythiophosphoryl group, 2-halogenated alkanoyl group, acyloxyacetyl group or alkoxyoxalyl group, R ^6 represents an alkyl group, a halogen atom, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkylthio group, an alkylsulfinyl group, an alkylsulfonyl group, a nitro group, or an amino group. (VI): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(VI) A compound represented by [in the formula, R^2 and R^6 represent the above] is heated to 0°C in the presence of a hydrogenation catalyst. Reduced at a temperature of 80°C by a method known per se to convert it into an amino compound,
Without further isolation of this amino compound, formula (III
): R^5Y(III) [In the formula, R^5 represents the above-mentioned one and Y represents a leaving group] and the compound represented by the formula (IV): R^7-NCO(IV) [In the formula , R^7 is an alkyl group having 1 to 4 C-atoms, a cycloalkyl group having 5 to 8 C-atoms, nitro, halogen, an alkyl group having 1 to 4 C-atoms or represents a phenyl group optionally substituted by alkoxy having 4 C-atoms.
IIa) Method for producing the tricarbonyl compound. (8) Formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^1 represents a hydrogen atom, a methoxycarbonyl group, an ethoxycarbonyl group, a methyl group, or a cyano group, and R^ 2 represents an alkyl group with 1 to 4 C-atoms, R^3 is an alkyl group with 1 to 4 C-atoms, an alkenyl group with 3 or 4 C-atoms, 3 or 4 R^4 represents a hydrogen atom or an alkyl group having 1 to 4 C-atoms; 5 is a hydrogen atom, an alkyl group, an aliphatic acyl group having 2 to 8 C-atoms, a formyl group, a cycloalkylcarbonyl group having 4 to 7 C-atoms, a methoxyalkylcarbonyl group, nitro, halogen, Benzoyl, alkoxycarbonyl, benzyloxycarbonyl, phenoxycarbonyl, alkylthiocarbonyl, N,N-dialkylcarbamoyl, N-alkylcarbamoyl, cycloalkyl optionally substituted with alkyl, alkoxy or haloalkyl N-cycloalkylcarbamoyl, N-alkoxy-N-alkylcarbamoyl, N-phenylcarbamoyl optionally substituted by nitro, halogen, alkyl or alkoxy, having 5 to 8 C-atoms in the radical group, alkylsulfonyl group, alkenylsulfonyl group, halogenated alkylsulfonyl group, N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group,
N-acyl- having 2 to 5 C-atoms in the acyl group
N-alkylsulfamoyl group, N-alkyl-N-methoxycarbonylsulfamoyl group, dialkoxyphosphoryl group, dialkoxythiophosphoryl group, 2-halogenated alkanoyl group, acyloxyacetyl group or alkoxyoxalyl group, R ^6 represents an alkyl group, a halogen atom, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkylthio group, an alkylsulfinyl group, an alkylsulfonyl group, a nitro group, or an amino group] and salts of this compound. Contains herbicides. (9) Inert additives and formula (I): ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^1 is a hydrogen atom, a methoxycarbonyl group, an ethoxycarbonyl group, a methyl group, or a cyano group. R^2 represents an alkyl group having 1 to 4 C-atoms, R^3 represents an alkyl group having 1 to 4 C-atoms, and R^3 represents an alkyl group having 1 to 4 C-atoms, R^4 represents a hydrogen atom or a halogenated alkenyl group or propargyl group having 3 or 4 C-atoms and 1 to 3 halogen substituents; R^5 represents a hydrogen atom, an alkyl group, an aliphatic acyl group having 2 to 8 C-atoms, a formyl group, a cycloalkylcarbonyl group having 4 to 7 C-atoms, methoxy Alkylcarbonyl group, benzoyl group optionally substituted with nitro, halogen, alkyl, alkoxy or haloalkyl, alkoxycarbonyl group, benzyloxycarbonyl group, phenoxycarbonyl group, alkylthiocarbonyl group, N,N-dialkylcarbamoyl group, N-alkylcarbamoyl, N-cycloalkylcarbamoyl having 5 to 8 C atoms in the cycloalkyl group, N-alkoxy-N-alkylcarbamoyl, substituted by nitro, halogen, alkyl or alkoxy; optionally N-phenylcarbamoyl group, alkylsulfonyl group, alkenylsulfonyl group, halogenated alkylsulfonyl group, N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group,
N-acyl- having 2 to 5 C-atoms in the acyl group
N-alkylsulfamoyl group, N-alkyl-N-methoxycarbonylsulfamoyl group, dialkoxyphosphoryl group, dialkoxythiophosphoryl group, 2-halogenated alkanoyl group, acyloxyacetyl group or alkoxyoxalyl group, R ^6 represents an alkyl group, a halogen atom, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkylthio group, an alkylsulfinyl group, an alkylsulfonyl group, a nitro group, or an amino group] and salts of this compound. Contains herbicides. (10) R^1 and R^4 represent hydrogen atoms, and R^5
represents a hydrogen atom, an acetyl group, or a benzoyl group, and R^6 represents a fluorine atom or a chlorine atom (
The herbicide according to claim 9, which contains the cyclohexenone derivative of I). (11) Formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [In the formula, R^1 represents a hydrogen atom, a methoxycarbonyl group, an ethoxycarbonyl group, a methyl group, or a cyano group, and R^ 2 represents an alkyl group having 1 to 4 C-atoms, R^4 represents a hydrogen atom or an alkyl group having 1 to 4 C-atoms, R^5 represents a hydrogen atom, an alkyl group, 2 Substituted by aliphatic acyl with ~8 C-atoms, formyl, cycloalkylcarbonyl with 4-7 C-atoms, methoxyalkylcarbonyl, nitro, halogen, alkyl, alkoxy or haloalkyl 5 to 8 C atoms in the benzoyl group, alkoxycarbonyl group, benzyloxycarbonyl group, phenoxycarbonyl group, alkylthiocarbonyl group, N,N-dialkylcarbamoyl group, N-alkylcarbamoyl group, or cycloalkyl group that may be N-cycloalkylcarbamoyl group, N-alkoxy-N-alkylcarbamoyl group, N-phenylcarbamoyl group optionally substituted with nitro, halogen, alkyl or alkoxy, alkylsulfonyl group, alkenylsulfonyl group having - atoms , halogenated alkylsulfonyl group, N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group,
N-acyl- having 2 to 5 C-atoms in the acyl group
N-alkylsulfamoyl group, N-alkyl-N-methoxycarbonylsulfamoyl group, dialkoxyphosphoryl group, dialkoxythiophosphoryl group, 2-halogenated alkanoyl group, acyloxyacetyl group or alkoxyoxalyl group, R ^6 is an alkyl group, hydroxy group, alkoxy group, alkenyloxy group, alkynyloxy group, alkylthio group, alkylsulfinyl group, alkylsulfonyl group,
A tricarbonyl compound represented by the following formula: nitro group or amino group.